Catalysts of oxidation for diesel engines based on base metals and modified with base metals

FIELD: chemistry.

SUBSTANCE: inventions can be used in field of environment protection. Method of catalyst obtaining includes introduction of base metal in form of ammonium hydroxide or ammonia complex, or in form of organic amine complex, or in form of hydroxide compound into active in redox reactions cubic fluorite CeZrO_x material under basic conditions. Catalyst of oxidation includes primary catalytic active metal from group of noble metals, applied on carrier, as well as secondary catalytic active component, which is obtained by ionic exchange between surface of cubic fluorite CeZrO_x material and base metal solution and optionally zeolite. Obtained catalysts are used in catalytic device, placing one of them on substrate, around which case is located. Obtained catalysts are also used in method of processing of exhaust gases, passing exhaust gases above them.

EFFECT: inventions make it possible to obtain catalysts for Diesel engines, possessing resistance to hydrothermal treatment and to action of poisons under conditions of system of emission of exhaust gases of Diesel engine, as well as to achieve high degree of conversion of pollutants at lower temperatures.

26 cl, 20 dwg, 4 ex

Introduction and background of invention

The emission of exhaust gases of motor vehicles is a significant source of air pollution, it makes a major contribution to the occurrence of photochemical smog and effects associated with ozone, which have a significant negative impact on human health (M.V. Twigg, Applied Catalysis B, t, (2007), p.2-25). So for the last thirty years has been more severe restrictions were imposed on the composition of the exhaust gases both gasoline and diesel internal combustion engines, for example, protocols Euro 5 or Euro 6 (statement of the European Parliament and of the Council No. 715/2007, adopted on 20 June 2007, Official Journal of the European Union L 171/1, see also Twigg, Applied Catalysis B, t. C.2-25, and R. Heck, R.J. Farrauto Applied Catalysis And t, (2001), 443-457 and references in these sources). The most significant gaseous emissions from motor vehicles contain pollutants such as carbon monoxide (CO), nitrogen oxides (NO and NO₂together they represent NOx), and unburned hydrocarbons (HC). In order to achieve the statutory requirements for removal of contaminants, the technology developed additional processing exhaust gases both gasoline and diesel engines. These technologies include, but are not limited to, methods of regulation/modification of engines, alternating cycles SG is Ganja and application systems additional processing, for example, catalytic control devices that remove contained in the EXHAUST gas pollutants by promotion of chemical reactions, aimed at the transformation of undesirable compounds in more environmentally friendly molecules. In the case of diesel engines /engines with compression ignition such devices include oxidation catalysts for diesel engines (CODE), diesel NOx trap/catalyst systems of storage of NOx (AMC/SHA), and a catalyst for selective catalytic reduction (SCR)are designed for processing of emitted CO, HC (CODE) and NOx, as well as catalytic diesel particulate filter (CDSF)designed for removal and burning of captured solids, also called particulate matter or soot.

Of the above catalytic systems for the regulation of the composition of the EXHAUST gas of diesel engines CODE is the most widely studied and applied technology (see, for example, US patents 5371056, 5462907, 6153160, 6274107, J.A.A. van den Tillaart, J. Leyrer, S. Eckhoffn E.S. Lox in Applied Catalysis In V.10, 1-3, p.53-68). Normal currently used CODE include heat-resistant oxide carrier, such as alumina, a component designed to capture/release of hydrocarbons, with the aim of improving operational performance at low temperatures, typically zeolite (Applied Catalysis B, t, 2007), C.2-25, Applied Catalysis And t, (2001), s-457) and active noble metal or metals, previously used platinum, and recently began to use a combination of Pt/Pd, as the main catalytically active materials, see U. Neuhausen, K.V. Klementiev, F.-W. Schutze, G. Miehe, H. Fuess and E.S. Lox in Applied Catalysis B: Environmental, t, 3-4, (2005), s-199 and are listed in the article links. The choice of these metals based on their ability to provide the highest speed of response (number of reactions per second) for the oxidation reactions of CO and hydrocarbons to CO₂and water at low temperatures and low concentrations of the active component in the composition for the CODE.

Requirements of the CODE and their ability to perform direct regulation of gas emissions increase over time, they must meet the new problems arising when legislative approval of each new generation of environmental requirements, for example, to have the ability to make efficient combustion is introduced after the engine HC necessary to generate short-term temperature increase, which triggers the regeneration of the DSF; later came the requirement that the filters could oxidize NO to NO₂to speed up the reactions in low-temperature SCR ammonia. Moreover, this flexibility must be provided without compromising the primary function of the OD-effective management of emissions, that is, the CODE must have the property of low-temperature ignition of the reaction. Thus, in addition to this versatility, the CODE must ensure that work at low temperatures to reduce emissions at cold start. This requirement is especially important when working in the field of low temperatures existing and next generation diesel engines, which are characterized by increased emissions of CO and HC, because the more intensively used EXHAUST gas recirculation or advanced combustion cycles, to reduce the content of NOx in the EXHAUST gas (patent WO/2005/031132, a Method and apparatus for high efficiency regulation of the EXHAUST gas of the internal combustion engine with direct injection, gas-fired). This task is even more complex due to the kinetic features of the oxidation of CO, in which high concentrations lead to a decrease in the rate of oxidation (A. Bourane, and D. Bianchi J. Catalysis 222 (2004) 499-510 and are listed in the article link). One final requirement is that the CODE must maintain a high activity after exposure to transient high temperatures in the presence of steam, as it occurs in a tightly-coupled catalyst or during active regeneration is required when the work of the DSF, as in these cases, the CODE is ejecta the heat of combustion of hydrocarbons, entered into the system afterburning after the engine.

In order to achieve the above purposes and in order to perform the necessary conditions for the operation of the engine, whose term of office comes to an end, it is necessary to increase the content of noble metals in normal CODE. In turn, this requires the use of high amounts of platinum and palladium, which leads to a further increase in the value of these precious metals and also excessive costs imposed on car manufacturers. To solve these problems requires an alternative, not as expensive catalysts based on precious metals, which could replace noble metals in relation to their catalytic action in the CODE, or to strengthen their action. These catalysts based on precious metals must have competitive properties: resistance to hydrothermal treatment and to the action of poisons under various conditions arising in the exhaust system of a diesel engine.

Summary of the invention

The present invention provides a new class of systems-based CODE base metals or modified base metals, which can solve the above problems. This improved technology is implemented by the introduction of a new generation of Mat is rials to store oxygen (JHC), in which the ion exchange introduced base metal, and provides a significant improvement in the operational characteristics of the device for low-temperature catalytic oxidation of CO, by itself or in combination with conventional CODE containing platinum group metals. The specific combination of catalysts for CO oxidation on the basis of modified MHC conventional catalyst based on platinum group metals (PGM) provides a synergistic effect, which makes it possible to achieve a high degree of transformation of pollutants at lower temperatures and with increased stability under hydrothermal conditions.

These new active in oxidation-restoration materials described in the application US 12/363310 and 12/363329, as well as in article SAE 2008-01-0481, as it was found, additionally create synergistic benefits in performance in the oxidation of CO, and the additional advantage is the provision of improved longevity in hydrothermal conditions, the CODE in relation to the temperature of ignition reaction conversion (temperature, which is required to achieve 50%conversion). Modified materials for HC in the present invention are systems based on solid solutions CeZrOx, containing essentially pure structure is the cubic phase type fluorite, get them by the introduction of base metals, i.e. metals not belonging to the group of noble metals, by special ion exchange. The range of suitable materials and all the details for carrying out ion exchange is described in other sources (patent application US 12/363310 and 12/363329). The method of ion exchange, not wanting to be limited to a specific theory, essentially includes the introduction of active metal /him cations in solid solution in the basic conditions, i.e. under conditions of high pH, i.e. at high content of HE^-/low content of hydronium ion (H₃About⁺) or proton (H⁺As shown in the previous work, the resulting materials exhibit high activity and stability under hydrothermal conditions in comparison with any modification carried out by conventional impregnation acid metal salt, for example, a metal nitrate, in which the ordinary is the formation of the bulk phases of oxides prepared materials and rapid sintering of these oxide phases, leading to deactivation. The proposed exchange of particles N⁺on metal ions makes possible the introduction and stabilization of specific monovalent ions, e.g., K⁺, divalent, for example, Cu²⁺, trivalent, for example, Fe³⁺and ions of higher valency at high dispersed the tee within the oxide matrix. The choice of input in this way, base metals based on known properties of their oxides, which are active in the reaction of particular interest or importance in catalytic respect. Metals of particular importance as catalysts include Ag, Cu, Co, Mn, Fe, alkali metals, alkaline earth metals or transition metals, or other metals or metalloids, which it is known that they form a stable nitrate NOx_{the BPA}that can undergo subsequent decomposition and recovery of N₂under conditions that are within the normal operating window of the EXHAUST gas of the vehicle. The term "transition metal" understand the 38 elements in groups 3 through 12 of the Periodic table of elements.

Materials for storage of oxygen (JHC) is a well-known solid electrolytes on the basis of, for example, solid solutions of oxides of cerium-oxide of zirconium (CeZrO_x). They are an integral component of catalysts for additional treatment of the EXHAUST gas of gasoline engines due to their ability to buffer the effect of the active components of the catalyst, preventing the emergence of local-enriched fuel (replacement) local or depleted fuel (oxidizing) conditions. Materials for HC ensure such action by highlighting the active oxygen is of the three-dimensional structure of the oxide quick and reproducible method in the conditions of transition modes when the gas phase depleted in oxygen, and lost the oxide during these processes oxygen is compensated by adsorption from the gas phase under conditions when in the system there is an excess of oxygen. This redox activity (hereinafter OB activity) is ensured by the existence of a pair OB CE⁴⁺→CE³⁺in which the oxidation state of CE depends on the local oxygen content. This high availability of oxygen is critical to the promotion of typical oxidation reactions/restore, for example, chemical transformations of CO/NO three-component catalysts for the petroleum (gasoline) engines, or that later developed, for the direct catalytic oxidation of solid particles (soot) in the catalytic DSF, see, for example, US 2005/0282698 A1.

Why are carried out intensive research aimed at the study of the chemistry, synthesis, modification and optimization of materials for the storage of oxygen on the basis of Ce-Zr. For example, the use of materials based on cerium - zirconium additives ions of low valency in applications related to the adjustment of the emission of the EXHAUST gas is intensively investigated in the US 6468941, US 6585944 and US 2005 0282698 A1. These studies have shown that modifying ions of low valency, for example, ions of rare earth metals such as Y, La, Nd, Pr, etc., transition metals, n is the sample, Fe, Co, Cu, etc. or alkaline-earth metals, for example, Sr, Ca and Mg may have a positive effect on the conductivity in relation to the oxygen ion. I believe that this action is due to the formation of oxygen vacancies in cubic crystal lattice in the solid solution, resulting in lower energy barrier for ion transport oxygen from the volume to the crystal surface, and increase the ability of the solid solution to the buffer effect at the time of regime change associated with the change in the ratio of air and fuel in the EXHAUST gas flow when the conventional three-component catalyst for gasoline engine.

Additionally it has been shown (in US patents 6468941 and US 6585944)that the use of specific examples of the above additives can provide full stabilization of the preferred cubic crystal lattice of the fluorite type in solid solutions of cerium oxide - zirconium oxide, and special benefits to the presence of yttrium. The presence of the preferred cubic structure type fluorite was found to correlate with the most rapid oxidation-reduction process CE⁴⁺→CE³⁺both on the surface and in the volume of the crystal lattice, thus greatly increasing the capacity in terms of storage and you the population of oxygen, compared with the volume of SEO₂. This advantage is especially pronounced in the case when the material is subjected to crystal growth/agglomeration during the occurrence of extreme hydrothermal conditions in a typical flow of the EXHAUST gas environment. Supplementation of yttrium and to a lesser extent La and Pr, as shown, also limits or, in certain cases, prevent disproportionation of a single cubic phase of cerium oxide - zirconium oxide in the composite, including enriched in cerium cubic phase and enriched the Zirconia tetragonal phase; this process leads to a significant reduction of the redox steps, specific surface, and deterioration of other characteristics of the solid solution.

Finally, in patents US 6468941, 6585944, 12/363 310 and 12/363329 describes the potential application of basic additives, that is, not belonging to the group of noble metals (Pt, Pd, Rh, Au, etc.) modifying metals, their inclusion in cubic fluorite crystal lattice of the solid solution by a direct method of synthesis (US 6468941, 6585944) or by ion-exchange modification after synthesis (bids US 12/363310 and 12/363329). Modification of the solid solution by such methods, as shown, represents an alternative way of promotion of redox reactions of cerium and Naib the additional interest is the application of Fe, Ni, Co, Cu, Ag, Mn, Bi and mixtures of these elements. Typical not promoted materials for storage of oxygen usually show high oxidation-reduction at about 600°C (determined on the basis of studies of temperature-programmed reduction with hydrogen (TPV)), and the inclusion of non-noble metals in the crystal lattice can lead to lower this temperature more than 200°C, at a much lower cost compared with the use of noble metals. Thus, by analogy, we propose that the same significant improvement in their ability to transport and reactivity equally applicable to the oxidation of CO, as it was observed in the case of the oxidation of N₂. Therefore, when these active oxides of base metals in normal CODE, it becomes possible to reduce the temperature required for ignition of the reaction in the presence of this catalyst.

However, while these base metals can benefit to enter into the crystal lattice CeZrOx and this introduction can significantly enhance the low-temperature redox activity of fresh materials, the addition of these elements may also lead to a decrease in the phase purity of the fresh and aged materials, as well as to a significant reduction of resistance to Hydra thermal effects (introduction base metals promotiom aggregation of crystals and the seal material) that is deteriorating behavior during aging compared with the basic compositions that do not contain additives and base metal. In addition, during normal aging cycles can proceed the reaction between the components of the gas phase and CeZrOx material, which can lead to the extraction of these additional elements composed of base metals of the cubic lattice of the fluorite type. This, in turn, can lead to the formation of a separate bulk phases (phases)with inherent low catalytic activity, or, in the case of the worst scenario phases, which can directly react with the storage of oxygen or other components of the catalyst, which leads to direct or indirect poisoning of the catalyst. Thus, until recently, required special precautions synthesis, allowing you to enter the modifier ions of low valency in cubic fluorite structure when saving as electroneutrality and composition phases. As shown in the application US 12/363310, synthesis of materials for HC containing specific modifier metal in a low valency (Ag), embedded in a cubic fluorite structure, containing about 40%of the mass. CE led to the disproportionation phases at sites enriched in CE, and areas depleted in CE, when C is ucitelem reducing OB properties. On the contrary, in the new developed method of ion exchange in basic terms it is possible to provide equivalent composition with high activity and hydrothermal stability for use in the catalyst control emissions from diesel engines. This combination of increased activity in the oxidation and stability under hydrothermal conditions provides, therefore, desirable to improve operational performance for industrial applications.

Benefits and features of the present invention include the following factors.

(a) providing Autonomous CODE, including base metal, or component composed of base metal capable of acting in a synergistic mode with the conventional technology CODE, with the aim of promotion of low-temperature oxylene WITH.

(b) Improved performance in respect to CO oxidation, due to the high dispersion promoting centers, including base metal, in the system CeZrOx, which leads to high availability for gaseous reagents active particles O.

(C) Providing an active component composed of base metal, capable of providing improved activity with equal content in relation to the component based on the noble metal, or equivalent performance with lower costs on the add / platinum group metals.

(g) Improved stability under hydrothermal conditions in comparison with the conventional structure of the CODE due to the high stability of the modifier is made of base metal.

(d) the Ability to benefit must obtain prior JHC with the necessary structural and textural properties, for example, single-phase cubic structure, mesoporous structure, high and stable pore volume and specific surface area, which provides further improvement associated with these operational advantages for subsequent modification.

(e) the Possibility of more flexible chemical modification with minimal disruption of the lattice parameters, phase purity, density of defects, surface acidity/basicity, etc.

(g) a Simple method for the synthesis provides the possibility of further modifications to the standard pre-existing sales materials with obtaining a set of materials with the required properties and characteristics, adjusted for a particular application.

This strategy differs from the one used in the synthesis of conventional systems, the CODE for which the inclusion of a component on the basis of base metal, for example, "three-dimensional SEO₂as catalytically active component, is described for the catalytic oxidation of the liquid portion of the solid h is STIC" (quote from R.J. Farrauto, K.E. Voss, Applied Catalysis B, V.10, 1-3, 14 (1996), p.29-51, see also US patents 5462907, 6153160, 6248684, 6255249 and 7078004). Therefore, the second new distinctive feature of the present invention is to include an active component for the direct oxidation of CO, with all the related advantage of the fact that atypical for the influence of addition of compounds for HC type CeZrOx on the hydrothermal stability of the compositions for the CODE.

Of course, the use of copper or other base metal (metals) in combination with cerium oxide is not a unique feature of the present invention. Such systems are widely investigated for a large range of applications, see, for example, J. Catal. t (2), 2005, C-475 (steam reforming of methanol on Cu/ZiO₂/CeO₂), Applied Cat. And, t, 2007, s.112-120 (modified PGM catalyst CuO-CeO₂selective oxidation of CO in the streams enriched in N₂or in Catalysis Comm. Vol.8 (12), 2007, C-2114 (oxidation of diesel soot mixture NO/ABOUT₂). However, in the present description it will be seen that as a way of introducing base metal, and the advantages possessed by these materials when the "real" application, are new.

In the present description is described catalysts, modifiers based on base metals and their uses. In one of the preferred options the catalyst oxidation viewlocity catalytically active material, deposited on a substrate. The catalyst is optionally include from about 10 to 50%massimodereerimisega base metal having a cubic fluorite the structure of component-based mixed oxide Ce-Zr, and from about 10 to about 50%mascherata, based on the total weight of the catalyst composition.

In one of the preferred variants of the catalytic device may include a housing, which surrounds the substrate, which caused the oxidation catalyst for EXHAUST gas of the engine with compression ignition. Also, the method of processing EXHAUST gas of the engine with compression ignition may include:

the flow of the EXHAUST gas of a diesel engine on the oxidation catalyst with compression-ignition; and oxidation of the component contained in the EXHAUST gas flow.

Catalytically active materials, including modified metal JHC, can be included in the composition by combining aluminum oxide, or other suitable media, with other catalytically active materials with the mixture, drying (active or passive) and optional calcination. More specifically, the suspension can be obtained by combining aluminum oxide, modified powder JHC and water, and optionally a means of regulating the pH (for example, inorganic or organic acids and bases) and/or other components. Catalyticallyactive materials (for example, catalytically active metals, e.g., platinum) can be added in the form of salts (salts) (for example, inorganic salts and/or organic salts). This suspension can then be applied in the form of a porous layer on a suitable substrate. Containing porous coating product can be dried and subjected to heat treatment to consolidate the porous coating on the substrate.

The catalyst may further comprise a zeolite. Possible zeolites include zeolite type Y, zeolite beta, ZSM-5, cranialfacial (SAPO, for example, SAPO34) and the like, and combinations comprising at least one of these zeolites. The ratio of silica to alumina (Si:Al) in the zeolite may range from about 15 to about 80, or, more specifically, from about 35 to about 60. If you use a zeolite, it can be added to the suspension together with a catalytically active material (e.g., before annealing catalytically active material).

This suspension can be dried and subjected to heat treatment, for example, at temperatures of from about 500 to about 1000°C., or more specifically from about 500 to about 700°C., with formation of the final catalytic composition. Alternatively, or in addition, the suspension can be applied in the form of a porous coating on a substrate and then subjected to heat treatment as described you the e, to adjust the specific surface area and crystalline nature of the medium. After heat treatment, the carrier may not necessarily apply catalytically active metals. Catalytically active metals, therefore, can be added after fixing the porous coating on the substrate through an additional stage of applying the porous coating and/or by affecting containing porous coating a substrate a fluid containing a catalytically active metal.

Caused the catalyst may include platinum group metals (Pt, Pd, Rh, etc.), (modified) alumina and zeolite, optional silicon oxide to which is added a modified metal JHC. The number of these components in the deposited catalysts can be any of the following: from about 0.1 to about 10%masses, from about 50 to about 80% of the mass. (modified) aluminum oxide, from about 10 to about 50 wt%. modified metal JHC, and from about 10 to about 50 wt%. zeolite; or, more specifically, from about 1 to about 5% of the mass. PGM, from about 40 to about 60%massimodereerimisega of aluminum oxide, from about 25 to about 45% of the mass. modified metal JHC, and from about 25 to about 45% of the mass. zeolite.

Caused the catalyst may be located on the substrate. The substrate may include any material, R is robotany for use in the required environment, for example, in the environment in the engine with compression ignition (e.g., diesel engine). Some possible materials include cordierite, silicon carbide, metal, metal oxides (such as alumina and the like), glass and the like, and mixtures comprising at least one of the above materials. These materials can be in the form of dense materials, extrudates, foil, pre-molded products, Mat, fibrous material, monoliths (e.g., a honeycomb structure or the like), other porous structures (e.g., porous glasses, sponges), foams, molecular sieves and the like (depending on the particular device), and combinations comprising at least one of the listed materials and forms, for example, metal foil, sponges aluminum oxide open pores, and a porous glasses with ultra-low-expansion. Moreover, these substrates can be coated with oxides and/or hexalite, for example, stainless steel foil, covered with a film of exhalent.

Although the substrate can have any size or geometry, in accordance with the above limits, the size and geometry are preferably chosen to optimize the specific surface for the structural parameters of the device control output from rabotavshih gases. Typically, the substrate has a honeycomb geometry, including cell passing through the channels having a cross-section in the shape of a polygon or circular, preferably is substantially square, triangular, pentagonal, hexagonal, heptagonal or octagonal geometry, or equivalent, thanks to the ease of manufacturing and increased surface area.

After applying the catalytically active material on the substrate, the substrate can be positioned in the housing with a receiving Converter. This casing may be of any design and may include any material suitable for this purpose. Suitable materials for the housing may include metals, alloys and similar materials, such as ferritic stainless steels (including stainless steels, such as, for example, 400 series such as SS-409, SS-439, and SS-441), and other alloys (for example, containing Nickel, chromium, aluminum, yttrium and the like metals, for example, to provide increased stability and/or corrosion resistance at operating temperatures or in an oxidizing or reducing atmosphere).

In addition, it is made of a material similar to the one used for the housings, tail cone (cones), end plate (plate), nozzle (nozzles) for piping for EXHAUST and similar devices may be concentric education is located around one or both ends to provide a sealed gas retention in the body. These components can be made separately (for example, by way of casting or the like), or can be manufactured as a single unit with the body, using techniques such as molding with rotation and such. A suitable device is shown in Nunan, US 2005/0129588 A1.

Between the housing and the substrate can be located retaining material. The retaining material which may be in the form of mats, granular material or the like, may be an intumescent material, for example, a material including vermiculite component, i.e. a component that expands when heated, and not the intumescent material, or a combination of both. These materials may include ceramic materials, such as ceramic fibers and other materials, for example, organic and inorganic binders and the like, or combinations comprising at least one of the above materials.

Thus, containing coating the monolith, including improved CODE containing modified metal JHC, injected into the EXHAUST gas flow of the engine with compression ignition. This provides a means of processing the specified flow of the EXHAUST gas of the engine with compression ignition to reduce concentrations of environmental toxins by passing the specified flow of the EXHAUST gas of the diesel engine over the above catalyst Oka is ing substances, contained in the EXHAUST gas in the total oxidizing (oxygen-rich) conditions to accelerate catalytic conversion / oxidation in a more environmentally friendly products.

The above-described catalyst and method and other features will be appreciated and understood by persons skilled in the art from the above detailed description, drawings and appended claims.

Brief description of drawings All compositions are given in wt. -%

JHC 1=40% CeO₂; 50% ZrO₂/HfO₂; 5% La₂O₃, 5% Pr₆O₁₁JHC 2=31.5% of CeO₂; 58,5% ZrO₂/HfO₂; 5% La₂O₃; 5% Y₂O₃JHC 3=44% CeO₂; 42% ZrO₂/HfO₂; 9.5% of La₂O₃; 4,5% Pr₆O₁₁Figure 1: comparison of data (for JHC 3 and modified by the introduction of 2% of the mass. Cu JHC 3. Figure 1 is a comparison of the behavior of temperature-programmed recovery N₂mixed oxide CeZrLaPrO_2-x(JHC 3) before and after carried out after synthesis of the main exchange with the aim of introducing 2%masse (hereinafter all samples will be designated as HME-MXK"Z", for example, 2Cu-MHC). Introduction copper (Cu) leads to a significant promotion OB properties JHC, and subjected to ion exchange material exhibits much stronger OB properties at temperatures below 300°C, compared to not subjected to ion exchange material, which is showing the maximum OB properties at about 575°C.

Figure 2: the ignition Temperature of the oxidation reactions of CO and HC in the SSG for 5Ag-MXK1 and 5Cu-MHC (each sample consisted of 0.5 g of zeolite beta at the entrance and 1.5 g of powder JHC output to simulate the actual installation CODE). Test conditions: 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% 02, 3,5% H₂O, else N₂, the heating rate of 12°C /min and 5 l/min

Figure 2 shows the data about the parameters of the oxidation reaction mixture simulating the EXHAUST gas of a diesel engine, in the reactor for synthesis gas (UCG).

The test conditions chosen to mimic the composition of the EXHAUST gas of the exhaust gases in accordance with Euro 5 standards, the train consisted of 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million N0, 3.5% of CO₂, 13% O₂at 3.5% N₂Oh, the rest of N₂, the heating rate of 12°C /min and 5 l/min Test was carried out using 0.5 g of the powder of zeolite beta (ratio of silicon oxide to aluminum oxide was 40), located at the entrance to the reactor, and 1.5 g of powder oxidation catalyst composed of base metal (fresh), located at the output, i.e. after the traps for hydrocarbon-based zeolite. The data confirm the efficiency of MHC, modificirovannogo the as copper, and silver, with catalytic oxidation WITH, and HC, and the first of the catalysts shows particularly good properties in CO oxidation.

Figure 3: the ignition Temperature of the oxidation reactions of CO and HC in the SSG 5 Cu-MXK1 and 5Cu-MXK2 (each sample consisted of 0.5 g of zeolite beta at the entrance and 1.5 g of powder JHC output to simulate the actual installation CODE). Test conditions: 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% O₂at 3.5% N₂Oh, the rest of n₂, the heating rate of 12°C /min and 5 l/min

Figure 3 shows the influence of the composition of MHC on the catalytic properties in a standard test in the UCG reactor, using conditions described in figure 2, for MHC 1 and MHC modified by the introduction of 5% Cu. Here again the two samples prepared as active in the oxidation of CO and HC, even in the absence of IPY. At this point, the oxidation WITH better going on 5Cu-MHC, which is consistent with a high content of CE in this material, and with the above concept of high activity in OB reactions in combination with the reaction of CO oxidation.

Figure 4: histogram, where the comparison of the ignition temperature of CO oxidation in the test on the ignition reaction in the reactor SHBG. Test conditions: 1000 ppm million, 600 h is Art./million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% O₂at 3.5% H₂O, else N₂, the heating rate of 12°C /min and 5 l/min

Figure 4 shows the ignition temperature CO oxidation for a set of modified ion exchange materials for HC in the test, SHBG, reused conditions shown in figure 2. All the samples tested showed good activity, except 1Au-MHC, which showed activity, more typical of normal, i.e. not modified MHC. The data also show that the ion exchange method, you can enter different modifiers at the same time while maintaining good activity. Therefore, the activity materials 1Fe-1Ag-1Cu-MXK1 and 1Ag-1Cu-1Co-MHC equivalent activity 5Cu-MHC, that is comparable indicators of activity are achieved with a lower content of the modifier. This shows the flexibility of this approach, and also opens the possibility of obtaining multifunctional oxides, for example, the introduction of the Ag with the aim of promotion of direct oxidation of soot, as in the bids US 12/363310 and 12/363329, and the introduction of Cu to maximize promotion of oxidative activity of copper.

In the initial tests yielded data on promising catalytic properties, so then held CPA is out activity 5Cu - MHC and sales of powder CODE containing only Pt (Pt content of 70 g/ft). The conditions of the experiment described in Fig, 2, except that the sample JHC was prepared on the basis of 0.7 g of zeolite beta (layer located before the main) and 1.3 g of powder 5Cu-MHC to obtain equal the content of the zeolite. In addition, the samples were subjected to aging in-situ in the reactor, SHBG, and their activity was investigated at different times of aging. Each stage of aging included keeping the sample in an atmosphere of reactive gas, the composition of which is shown in figure 2, with increasing temperatures, the components 700, 750, 800, 850 and 900°C, for 4 hours at each temperature. In all cases the temperature in the catalyst bed was monitored and it was found that she was at about 10-15°C higher than the oven temperature that is explained by fuel combustion (CO and HC) in the reaction gas mixture. From the comparison shown in figure 5, shows the following. Although the figures for fresh Pt CODE is much better, however, after high-temperature aging is not. After 4 h of aging at 700°C Pt CODE not only shows a small advantage, but after adding the second cycle of aging (4 h at 750°C) catalytic properties of the two materials are the same, the same is observed after aging at 800°C. it Should be noted that the catalytic properties of mo is inficirovannyh JHC not deteriorate in comparison with the properties of fresh catalyst after successive stages of aging at 700 and 750°C. Tighter aging at 850 and 900°C leads to a more significant deactivation of the catalyst 5Cu-MHC. This explains the decrease of the specific surface in such hard conditions. However, used in the testing conditions of hydrothermal aging, appears to be more hard compared to any extreme hydrothermal conditions in relation to time and temperature, which are created in real operating conditions of the motor vehicle. Despite this observation, it should be emphasized that the characteristics of the catalyst, including base metal, equivalent to the characteristics of the sales CODE platinum-based, and this result has important value.

Figure 5: Comparison of 5% of the mass. Cu-MHC and normal CODE containing 70 g/m Pt in testing the ignition reaction and aging (each sample consisted of 0.7 g of powder of zeolite beta at the entrance and 1.3 g of the reactive powder catalyst at the outlet in order to simulate the actual installation CODE).

Test conditions: 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% O₂at 3.5% N₂Oh, the rest of n₂, the heating rate of 12°C /min and 5 l/min

Indicate "After 700" and "After 750" refers to aging for 4 h in actionnow gas temperature at the inlet 700/750°C.

Fig.6: Comparison of 5%masspike Cu-MHC mixed with Pd CODE (35 g/m) CODE and containing 70 g/ft³Pt in testing the ignition reaction and aging (each sample consisted of 0.7 g of powder of zeolite beta at the entrance and 1.3 g of the reactive powder catalyst at the outlet in order to simulate the actual installation CODE).

Test conditions: 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% O₂. 3,5% H₂O, else N₂, the heating rate of 12°C /min and 5 l/min

Indicate "After 700" and "After 750" refers to aging for 4 h in the reaction gas mixture at the temperature at the inlet 700/750°C.

The advantages of the modified base metal JHC in CO oxidation is additionally shown in Fig.6, where the comparison of the operational characteristics of the CODE with a platinum content of 70 g/m and a mixture in the ratio 1:1 powder CODE containing 70 g/m of platinum, and sample 5Cu-MHC, that is, in this mixture, the effective content of platinum was 35 g/ft. Aging and testing was carried out as in figure 5. Here again the sample containing 70 g/m of platinum, fresh exhibits the best performance, although considerably reduced in comparison with the powder containing only base IU is all. However, after aging the opposite is true. So, T₅₀CO oxidation activity in CO oxidation of the mixed sample containing both platinum and base metal below at 15-18°C, compared with the sample containing 70 g/m of platinum, that is, are superior catalytic properties at lower concentrations of PGM by 50%. Moreover, the mixed powder does not detect significant decontamination after aging at 850 and 900°C, which we explain the synergistic action of platinum and base metal, which prevents a sharp drop in specific surface modified MHC, which, apparently, is accelerated by the exothermic combustion of the fuel molecules at high temperature.

Fig.7: Comparison 5Cu-MHC mixed with Pt CODE (35 g/ft³), with CODE containing 120 g/m of platinum, in the tests on the ignition reaction and aging (each sample consisted of 0.7 g of powder of zeolite beta at the entrance and 1.3 g of the reactive powder catalyst at the outlet in order to simulate the actual installation CODE).

Test conditions: 1000 ppm million, 600 ppm million C1 n-octane, 180 frequent./million of C1 methylbenzol, 75 ppm million of C1 propene, 75 ppm million C1 methane, 80 ppm million NO OF 3.5% CO₂, 13% O₂at 3.5% N₂Oh, the rest of N₂, the heating rate of 12°C /min and 5 l/min

Indicate "After 700" and "the Settlement of the e 750" refers to aging for 4 h in the reaction gas mixture at the temperature at the inlet 700/750°C.

7 additionally shows the perspectives of a sample of 5% Cu-MHC - 35 g/ft³Pt in testing SHBG. Here, the comparison of this mixture with the sample CODE containing 120 g/m of platinum was again applied the test protocols and aging, is shown in figure 5. In this case, the sample CODE with a high content of platinum exhibits the best catalytic properties used in all conditions, but with a significant increase in costs in relation to the content of PGM. Analysis of 5-7 suggests that, on the basis of detailed studies of catalytic activity in SHBG and aging advantages in performance for 5Cu-MHC are the same as for normal CODE, containing 60 g/m of platinum, have found a significant potential for saving costs.

Fig: the Influence of the content of SOx on the core features of the CODE in the tests on the ignition reaction in the reactor RESS.

Test conditions:

Runs 1/2: 1000 ppm million, 375 frequent./million With C1₃H₆, 300 ppm million NO, 8% CO₂10% of N₂About 5% of O₂rest N₂, the heating rate of 12°C /min and 5 l/min

Runs 3/4: the composition of the mixture is the same+5 frequent./million SO₂(corresponds to a content of 50 ppm million masses. sulfur in the fuel).

Previously we demonstrated the advantage of the present invention in relation to hydrocarboncontaminated, the next stage was to investigate the resistance to SOx poisoning. First, these properties are investigated in SHBG. In these trials containing porous coating cores monoliths (from 0.75 to 1 inch) tested in artificial mixtures, similar to the composition of the EXHAUST gas containing 1000 ppm million, 375 frequent./million With C1₃H₆, 300 ppm million NO, 8% CO₂10% of H₂O 5% O₂rest N₂, the heating rate of 12°C /min and 5 l/min. Temperature ignition using each core was determined twice used this mixture, and then two more times using a mixture, to which was added 5 frequent/million SO₂to cause poisoning SOx (5 frequent./million SO₂corresponds to 50 part./million mass, sulfur content in the fuel). Fig, 8 shows the tests of the three cores a, b and Sceniczny And included CODE containing 60 g/ft³Pt/Pd (60 at a ratio of 2:1, or 40 g/ft³Pt and 20 g/ft³Pd), it was applied a second layer comprising 2Cu-MHC and zeolite beta. The core had the same composition and structure, except that the content of PGM was 60 g/m at a ratio of 1:5, i.e. it contained 10 g/m of Pt and 50 g/ft Pd. The core had the same structure and the ratio of the oxides of base metals, however, this sample did not contain platinum group metals. Before testing, all samples were subjected to is whether stabilization by aging for 1 h at 650°C in the reaction gas mixture, does not contain SO₂. Data on pig show several striking features. First, the catalytic properties of the 2Cu-MHC significantly worse than in previous tests. This is explained by differences in the types used in the composition of the reaction gas hydrocarbons, that is, in the latter case, the applied mixture, in which a single hydrocarbon component was propene in high concentrations. In this case, the zeolite does not interact with the molecules of hydrocarbons and therefore, the preferred adsorption takes place on the active sites of the MHC, which prevents the access FROM and leads to a significant inhibition of the oxidation of CO. In addition, with the introduction of SO₂the core, as can be seen, undergoes gradual and catastrophic deactivation. This reflects the particular characteristics of the sensitivity of the active centers on the basis of copper contained in the material. On the contrary, if 2Cu-MHC used in conjunction with the IPY, there is a high activity catalyst. So, for the core And catalytic properties of highly stable and reproducible, all obtained values of T₅₀are within experimental error. The activity of the core is slightly smaller and the catalyst undergoes some systematic decontamination with increasing number of runs, especially after the introduction of SO₂that is explained by the higher senses the activity of the palladium to the SO ₂compared with platinum. However, activity is still relatively high, therefore, believe that when used in vehicles, the combination of a modifier composed of base metal and PGM will probably give the best results.

Figa: Torque aging and testing for initial samples: behavior in CO oxidation. Test conditions: Temperature SW 400°C/1000 frequent./million WITH/ 200 ppm million HC (C1) / 250 ppm million NOx/linear heating rate of 20°C/min, flow=1000 (MCOS approximately 85 hours).

Torque aging: SOx - 270°C at the inlet - 3250 rpm 25 Nm when the sulfur content in the fuel is 500 ppm million 650°C aging - 650°C, the temperature at the input to the CODE - 3500 rpm 220 Nm installation of the engine.

Figb: Torque aging and testing for initial samples: behavior in the oxidation of hydrocarbons. Test conditions: Temperature SW 400°C/1000 frequent./million WITH/ 200 ppm million HC (C1) / 250 ppm million NOx/linear heating rate of 20°C/min, flow=1000 (MCOS approximately 85 hours).

Torque aging: SOx - 270°C at the inlet - 3250 rpm 25 Nm when the sulfur content in the fuel is 500 ppm million 650°C aging - 650°C, the temperature at the input to the CODE - 3500 rpm 220 Nm installation of the engine.

On figa and 9b shows a torque behavior of full-size samples (4 inches in circumference, 6 inches in length, 40 cells per square inch) CODE of porous coatings And, B and C in comparison with the technology, which was used a catalyst comprising 70 g/ft²platinum. All samples were tested after aging in an oven (700°C, 10% water vapor, air, within 25 h), after aging for 20 hours in a torque mode in the flow of EXHAUST gas from the cycle of combustion using fuel containing 500 ppm million S, and finally after desulfuromonas / additional hydrothermal aging again in diametrically mode, the sample was kept in the stream of hot EXHAUST gas for 5 hours at a temperature input CODE 650°C (note that this aging was carried out using standard diesel fuel with ultra-low sulfur content). The data reflect the dependencies found when testing in SHBG presented on Fig. Again the catalyst 2Cu-MHC, not containing PGM shows low activity, the ignition of both reactions, CO and HC, does not leak in any of the investigated cycles of testing or aging. This confirms the strong inhibition of the catalyst composed of base metal toxic molecules HC and SOx contained in the EXHAUST gas. In contrast, the catalytic properties of samples a and b again are much better. When all the conditions of the activity in CO oxidation of the sample And exceeds the activity of the comparative sample, and this occurs when knowledge is sustained fashion lower PGM content. The behavior of the sample in CO oxidation also curious about the activity coincides with the comparative sample, despite the low content of platinum and the ratio of Pt:Pd, which is usually considered unfavorable. Of equal interest are the trends in activity in the oxidation of HC for samples containing PGM. For the sample with platinum concentration 70 g/m ignition reactions of hydrocarbons occurs at values close to T₅₀WITH, apparently, the process of ignition of both fundamental reactions involved, because in General the active centre. On the contrary, there is a noticeable difference between T₅₀WITH and ignition reaction In In for samples a and B. In both cases, the ignition of the reaction occurs at a temperature of 10-25°C lower than the ignition reactions of hydrocarbons that explain the advantages of using powder 2Cu-MHC for CO oxidation, which leads to increased activity, which is not observed for the oxidation of hydrocarbons, because this process requires other active centers.

Figure 10: Comparison of operating characteristics of the original samples in the car. Figure 10 is confirmed based, obtained by dynamometer testing of specimens presented on figa/9b, in the test car (data show activity after cycle aging in an oven at 700°C). Again containing only negative is natural metal sample (sample C) shows poor activity in the oxidation of CO and HC. In contrast, sample A (2Cu-MHC containing 60 g/ft³Pt/Pd ratio of 2:1) shows certain advantages in catalytic activity in the oxidation of CO, which can be seen from the improved results of the tests ECE (urban driving cycle), that is, are the benefits of cold start /lower the ignition temperature of the reaction. Finally, the sample (2Cu-MHC mixed with 60 g/ft³Pt/Pd ratio of 1:5) shows the excellent properties, which again is not consistent with the type of noble metal and its contents.

11: reactivation after aging in the presence of SOx sample (60 g/m³Pt/Pd ratio of 2:1), taken after the initial test. Torque aging and test conditions are the same as on figa/9b.

Another very interesting observation can be done by examining the data on figa/b: change of the sample after aging in SOx and subsequent removal of SOx/limited hydrothermal aging (5 h, 650°C). Figure 11 shows curves ignition CO oxidation after the initial aging in the oven, sulfotyrosine and desulfuromonas. Influence of sulphur and obviously no doubt, but at the same time, you can see that after subsequent hydrothermal aging activity is restored almost completely. This effect we refer to as light de is sulfirovaniu not only active centers on the basis of PGM but especially centers 2Cu-MHC. This effect will be investigated in more detail in the following drawings.

Fig: Torque aging and testing. The use of layered block/zone to overcome catastrophic deactivation component composed of base metal 2Cu-MHC (sample C). Torque aging and test conditions are the same as on figa/9b.

Because the sample containing only 2Cu-MHC showed unacceptably low activity were conducted additional torque aging and testing. In these tests the activity of the sample length of 6 inches, containing 70 g/m of Pt, was compared with the activity of a sample length of 3 inches, containing the same amount of platinum, as well as with the sample, after which the layer length of 3 inches, containing 70 g/ft³Pt was set to layer, length 3 inches, containing 2Cu-MHC, as well as with the sample, after which the layer length of 3 inches, containing 2Cu-MHC was set to layer, length 3 inches, containing 70 g/ft³Pt. Research will establish whether the apparent synergistic effect also in the case when applied layered arrangement of catalytic systems, i.e. in the way separate unit. Data on Fig confirm that this synergistic effect may occur when layered design is the block. The catalytic properties of the sample 3 inch 70 g/ft Pt/ 3 inches 2Cu-MXK3 much better than catalytic properties as sample 3 inch 70 g/m of Pt, and sample 3 inches 2Cu-MHC/3 inch 70 g/ft³Pt; these data confirm that the zone containing the usual CODE that allows you to protect the active centers of the catalyst on the basis of the base metal from the toxic effects of components of the EXHAUST gas, thus creating the opportunity for the second layer (composed of base metal) could provide an additional function for CO oxidation. Described fails to reverse the configuration of the block, because the activity of the sample 3 inches 2Cu - MHC/3 inch 70 g/m Pt and sample 3 inch 70 g/ft Pt coincide within experimental error.

Fig: Comparison of behavior in the torque of the aging and testing shows the benefits of applying 2Cu-MXK3 compared with the use of only MHCS and comparative CODE.

Test conditions:

Euro 4 test on ignition=SW temperature of 400°C/1000 frequent./million WITH/200 ppm million HC (C1)/250 ppm million NOx.

Euro 5 test on ignition=SW temperature of 400°C/2250 frequent./million WITH/750 frequent./million, HC (C1)/50 part./million NOx.

A linear heating rate of 20°C/min, flow=1000 (MCOS approximately 85 h^-1).

Torque aging:

DSF regeneration/aging with introduction after the engine, on the basis of the two is eklow:

And 10 min at 600°C at the entrance, 3550 rpm./min, 250 Nm engine installation. In 10 min at 400°C at the entrance, 750°C in the layer, after introduction of the engine, 2950 rpm./min, 110 Nm installation of the engine.

To further demonstrate /to distinguish benefits from the introduction of modifying additives was carried out a direct comparison of the advantages in catalytic properties 2Cu-MHC and MHC without modification. The results are shown in Fig. You can see that the catalytic properties of the usual CODE containing 90 g/ft Pt/Pd in a ratio of 3:1 CODE, containing 90 g/ft Pt/Pd in a ratio of 3:1 and MHC, after aging the same when using both standard testing protocols of the ignition reaction. In contrast, for the sample containing 90 g/ft Pt/Pd in a ratio of 3:1 and 2Cu-MHC, the temperature of half-transformation WITH approximately 7-10°C lower, depending on the test Protocol. Since all the samples were selected on the basis of approximately the same metal content, and aging cycles for all samples were the same, it is clear that the benefits generated by the promoting effect occur only as a result of the modification of MHC-precious metal, and not as a result of using the standard JHC.

Fig: Torque aging and testing of initial samples in comparison with the sales PtPd CODE 60 g/ft Pt/Pd in zootoxin and 2:1 (sample D). Torque aging and the test conditions were the same as described in figa/9b and Fig.

To reiterate the advantages of using 2Cu-MHC were conducted additional torque aging and testing using selected samples from those described in figa, and a sample containing only the primary metal (sample C) was replaced by sales PtPd CODE 60 g/ft³Pt/Pd ratio of 2:1 (designated as sample D), i.e. it is equivalent to a sample And in relation to the content of PGM. On Fig shows catalytic properties in successive cycles aging hydrothermal subsequent introduction/filter regeneration. From the given data one obvious benefit of application of the component containing the base metal, the ignition temperature of the reaction in the presence of the sample And on 8-25°C lower, depending on the specific conditions of aging and species mixtures that mimic the composition of the EXHAUST gas (Euro 4 or 5). Of additional interest is the comparison of the sample and containing 70 g/ft³Pt comparative sample; previously the comparative sample showed higher activity, but if you apply more stringent conditions of aging, the sample containing a high content of PGM and base metal begins to surpass the properties of the comparative sample, and the benefits of the its application becomes more obvious in the case when using more stringent conditions for the ignition of the fuel standard Euro 5.

Fig: comparison of the 2 trials in the car. Comparison of PtPd CODE 60 g/ft Pt/Pd ratio of 2:1 (sample a-60 + base metal) after aging in an oven shows the benefits of applying a containing 2Cu-MHC sample compared with the comparative. On Fig comparison of the techniques described on Fig, in a standard test in the car. Here is confirmed the benefits of applying a sample (60 g/ft Pt/Pd ratio of 2:1, containing base metal in the form of 2Cu-MHC), compared with the sample containing 60 g/ft Pt/Pd ratio of 2:1 and not containing base metal (tests conducted after aging in an oven). Again increased activity is attributed to the higher efficiency of conversion during ECE, i.e. to increased activity in the ignition reaction.

Fig: Torque aging and testing: comparison of CODE with low PGM content. Torque aging and the test is performed under the conditions described in figa/9b.

An additional test of this concept was conducted with a low total PGM content to determine the degree of promotion of operational characteristics at critical conditions. As you can see from Fig, the use of component-based base metal ensures that b is more strong decrease in the total PGM content and change its type. Since all three contain 2Cu-MHC sample, i.e. the sample a (containing 60 g/ft³Pt/Pd ratio of 2:1) sample E (containing 21 g/ft Pt/Pd ratio of 2:1) and sample F (30 g/ft³Pt/Pd ratio of 2:1), provide comparable characteristics with a reference sample containing 70 g/m Pt. Of course, in addition to the above high performance sample And the data presented here confirm that the sample F exhibits properties similar to those of the reference sample, with a further reduction in the concentration of PGM by 50% compared to sample A. This improved performance similarly exceeds the benefits that can be attributed only to the action of PtPd, which is reflected in significant decontamination effect of SOx poisoning and subsequent restoration of properties after hydrothermal aging.

Fig: Torque aging and sample tests comparing G to 30 g/ft³PtPd in the ratio 2:1 with samples containing 2Cu-MHC in the form of a separate layer (sample F) or in the form of a single layer (sample N).

Torque aging and the test is performed under the conditions shown in figa/9b and Fig.

On Fig comparison of dynamometer aging and behavior during testing of the sample F (30 g/m PtPd in the ratio 2:1, as the second layer in it sod who was realse 2Cu-MHC and zeolite) with the sales sample G, obtained in comparative technology (30 g/m PtPd the ratio 2:1), and sample H (30 g/m PtPd the ratio of 2:1, contains 2Cu-MHC in the same layer, which are IPY, alumina and zeolite, but its content was 50% of the content in the sample F). Again the samples contained 2Cu-MHC, after aging in an oven showed the best performance compared with the reference sample, and was more active sample F, which is consistent with the higher content of modifier. After aging in SOx all samples showed similar properties, because of the poisoning of non-precious metal, that is, in the poisoned samples active only PtPd, and therefore, all samples have the same activity, because they contain the same MPG in the same concentrations. After further hydrothermal aging and is associated with the SOx removal process samples containing 2Cu-MHCS, restore its significant activity, and again a number of activity corresponds to the number of deposited modifier composed of base metal. Finally, after aging cycles occurring in the regeneration of the filter, only a sample of F, as can be seen, retains significant advantages compared with the comparison sample. Apparently, the combination of aging after entering the sample containing mixed the e PGM and base metal in the same layer, undesirable and leads to a significant loss in performance. Thus, we can conclude that although the modifier based on the base metal can be used as a common layer with a material containing PGMs, this configuration is not suitable for applications in which the CODE should speed up the regeneration of the DSF. However, equally clear that, if you need to regenerate the DSF, in this case, the use of a layered structure of a catalyst comprising a layer containing PGMs, and the layer containing a base metal, is not only acceptable, it is actually again means getting significant advantages in performance compared to the conventional design CODE.

Fig: Torque aging and testing, comparison of the impact of SOx poisoning and their removal on the properties of the comparative sample containing only platinum, only 70 g/m Pt and 2Cu-MHC, and the sample containing PtPd and 2Cu-MHC. Torque aging and the test is performed under the conditions described in figa/9b.

Again, you notice that a particularly interesting feature of the catalytic properties of the CODE, the modified base metal, is their reaction to SOx poisoning. This process was investigated in more detail, the data shown in Fig. Here the activity of the sample, soderjaschegosya platinum in the amount of 70 g/m, comparable to the activity of the sample containing 70 g/m Pt and 2Cu-MHC (second layer), and a sample containing 120 g/m PtPd in the ratio of 3:1 (in this sample, again modified MHC was in the second layer). Both samples show improved activity after 20 h dyno aging at 650°C (T₅₀the oxidation of CO at 5-12°C below), as in the earlier data. Also consistent with the data shown above, the observation that this advantage disappears after aging in SOx. In fact, in this case, both samples containing base metal, showed the worst catalytic properties, compared with the comparative sample after 20 h of aging in SOx. It should also be noted that aging in SOx leads to loss of activity of the sample containing only platinum, but this loss is only part of the decline in activity, which is observed for samples J and K, and this higher resistance to poisoning because of a lack of 2Cu-MHC modifier. However, after a short heating of these samples, in this case for 15 min at the inlet temperature of 650°C (to simulate the regeneration cycle DSF), is restored to its original high level of activity in both samples. As regeneration proceeds as for samples containing PtPd, and for samples containing only platinum, this effect cannot be explained by conventional regeneration, which is observed for sample PtPd after cycle desulfurization, it must be the result of desulfurization 2Cu-MHC. Then carried out a second cycle of heating up to 650°C for 15 min, but all samples show similar catalytic activity within experimental error, in comparison with the previous test and the test conducted before the impact of SOx. These observations suggest that desulfuromonas component composed of base metal flows quickly and easily and this process can be entered in the normal operating cycle of the engine, i.e. the impact of SOx will be a little poison the active centers of the component on the basis of base metal, responsible for the oxidation of CO, but the sample will not be subject to full decontamination because of the periodic regeneration of the DSF will be sufficient for full recovery /desulfuromonas Cu-MHC.

Fig: Torque aging and testing, the impact zone of the coating on the SOx poisoning, desulfuromonas during ignition of the reaction and after hydrothermal aging CODE samples containing 30 g/ft Pt/Pd ratio of 2:1. Torque aging and the test is performed under the conditions described in figa/9b.

Fig: Torque aging and testing, the influence of zonal the CSOs coating on the SOx poisoning, desulfuromonas during ignition of the reaction and after hydrothermal aging of samples CODE containing 30 g/ft Pt/Pd ratio of 2:1. Torque aging and the test is performed under the conditions described in figa/9b.

On Fig and 20 additionally shows the characteristics when the SOx poisoning and desulfuromonas for material 2Cu-MHC. In this case, the influence of coverage and, more specifically, areas of coverage on properties in CO oxidation compared with the SOx. On Fig we compared the four samples, all of them contained 30 g/ft³Pt/Pd ratio of 2:1, one of them was a sales sample comparison, not containing 2Cu-MHC, and the remaining three samples contained 50% of the second area of the layer containing the modifier based on the base metal. First, this sample L with the "correct" orientation, that is, the zone in which the present base metal/zeolite located at the entrance; then the sample L in "reverse" orientation, i.e. the area containing base metal/zeolite is output; at the same time, the sample M, contained a modifier composed of base metal only on the input, i.e. in the "correct" orientation. All samples costarelli for 20 h at 650°C and then subjected to aging for 2 h in the presence of SOx, and determined the ignition temperature CO oxidation in two consecutive tests with a linear heating (i.e., the sample was heated in a stream of reaction is ionic gas from about 150 to about 350°C. at a linear heating rate of 20°C/min using a standard device with heat exchanger). The data show two interesting trends. First, the modified base metal CODE does not show the same degree of decontamination, which was observed in previous cycles, aging in the presence of SOx, for example, on Fig. You can see that all three of the tested sample still provide a significant reduction of the T₅₀then there is the use made of base metal in a separate area can provide advantages in the implementation of aging cycles involving SOx. Secondly, there is a significant improvement T₅₀the oxidation of CO from run 1 to run 2 for both samples, the resulting technology L. Comparison of results obtained after the values of T₅₀after further aging for 1 h at 650°C shows similar catalytic properties (within the limits of experimental error). That is, apparently, for sample L in either direction of flow for the removal of the principal amount of SOx and restore full activity 2Cu-MHC enough temperature, component 350°C. in Addition, the data suggest that the "reverse" direction of arrangement of the layers in the body can provide additional advantages in catalytic properties, especially in respect to the tion to the effects of SOx. On the contrary, the influence of repeated runs is much less significant for the comparison sample and the sample M, for which the majority of the observed values of T₅₀are within the experimental variance.

On Fig presents the results of more intensive aging in the presence of SOx the same samples, which are shown in Fig. Samples costarelli for an additional 20 h in SOx, and then they were tested with repeated increases in temperature. In this case, re-activation, as it was found, expressed to a lesser extent, and only to the sample L-back arrangement of the layers showed statistically significant values of regeneration after the first temperature increase. However, in this case, all three samples contained 2Cu-MHC have shown previously observed attenuation properties against aging in the presence of SOx, all of these samples were comparable or better than the comparison sample, which confirms that the location of the catalysts in the form of zones is suitable for such cycles aging. Moreover, after aging with the use of 100 cycles of regeneration of the DSF can clearly see a higher hydrothermal stability, which provides an introduction to CODE modifier composed of base metal, and the reduction of To for sample L in the reverse configuration extending t is from 6 to 16°C, that is, this sample provides the best catalytic properties.

Detailed description of the invention the Present invention relates to the development and application of modifiers on the basis of base metals in the catalysts for EXHAUST treatment. Modifier composed of base metal obtained from almost pure cubic phase of a fluorite type (which is determined by the xfa) type CeZrOx, well known in the art. This source material is subjected to subsequent modification by the introduction of base metal, for example, transition or other metal, as described in patent applications US 12/363310 and 12/363329. Not wanting to be limited by theory, believe that this modification occurs in the ion exchange of hydroxyl groups CE³⁺HE is present on the surface and to a lesser extent in the crystal, base metal/ion selected for this purpose, and leads to a significant promotion redox properties / ionic conduction of oxygen in CeZrOx.

Modified base metal materials CeZrOx /modifier based on the base metal can be advantageous to use catalysts regulation of the composition of diesel EXHAUST (or other depleted fuel) engines. The specific example described herein is described and, the use of such materials in the field of catalytic oxidation (especially CO and HC. This new generation of modified materials for HC, as shown, has a special advantage because it has the best catalytic properties at low temperature oxidation of CO and HC compared to non-modified MHC.

It should be noted further that the expression "first", "second" and similar in the present description does not indicate order of importance, they are more likely to distinguish one element from another, and a single or plural does not limit the number, but rather indicates the presence of at least one of the enumerated objects. Moreover, all the intervals described in the present description, are common and combinable (e.g., intervals of up to about 25 wt. -%, when the desired interval from about 5 to about 20 wt. -%, and more desirable from about 10 to about 15%of the mass. are inclusive of the endpoints and all intermediate values of these intervals, for example, from about 5 to about 25 wt.% of, "from about 5 to about 15 wt.% of etc).

Method of producing metal promoter is called a metabolism in basic conditions to improve the reaction of oxidation - reduction. This process describes how to modify an ordinary cm is Shannah oxide based on cerium and zirconium, also known as materials for storage of oxygen (JHC). The method includes processing JHC main, if possible, an ammonia solution of the modifying metal. Base metals, i.e. common metals that are usually used in this way include, but are not limited to, transition metals, such as silver, copper and cobalt, alkali metals such as potassium, alkaline earth metals such as calcium, strontium, barium. In those cases when it is necessary for ion exchange base metal does not form a stable air-ammonia complexes, for example, in the case of aluminum and iron, it is possible to apply a stable core complexes with organic amines. The term "transition metal" in the present description see 38 elements in groups 3 through 12 of the Periodic table of elements.

Variables of the method include (1) the selected MHC/mixed oxide; (2) used base metal, and (3) the concentration of this metal. Successfully applied metal concentrations are in the range from 0.02 to 5.0%massadah, at higher concentrations of metal in the exchange may be formed of bulk oxides of these metals, which does not preserve the synergistic combination with the use of JHC. Therefore, the most preferred concentration of metals introduced method the m ion exchange, amount from 0.1 to 2.5 wt. -%

Base metals are usually purchased in the form of a salt or solution of a metal salt, such as nitrate. As indicated above, most base metals form soluble complex with ammonium hydroxide. In cases where ammonia complex is unstable, instead of ammonium hydroxide can be applied organic amine, such as triethanolamine. In the described method the solution is acidic metal salt is converted to the main form when adding as the basis of ammonia-based solution of ammonium hydroxide at high pH, e.g., from 8.0 to 9.5. Proceeding with the reaction and the amount used of the base is changed depending on the applied metal. The resulting solution was used then for impregnation of powder mixed oxide thus subjected to ion exchange surface and subsurface hydroxyl group Xie HE (the outputs of the crystal lattice on the surface and bulk defects in the synthesis conditions act as the acid sites). This exchange process is believed, provides improved redox behavior modified in such a way that the mixed oxide. Saturated mixed oxide must first be calcined at a temperature sufficient to decompose inorganic anions (e.g., nitrate of ammonium ions), usually at temperatures above 350°C. In the calcination added the modifier metal is associated in those places where there were centers Xie HE.

Mixed oxide/JHC according to the present invention includes any known or potential ceritadewasa or containing cerium and zirconium stable solid solutions. Preferably the solid solution comprises a cationic lattice with a single phase that is determined based on the standard method of x-ray phase analysis. More preferably, this single phase has a cubic structure, and most preferably cubic structure of fluorite type. Additionally note that this ion-exchange process can be performed without additional education for the bulk phase, which is determined on the basis of XRD, so that the concentration of the introduced ion exchange of the cation does not exceed "concentration" centers Behold-HE is in a cubic crystal lattice of the fluorite type. In various preferred embodiments, MHC may include such materials for HC, which are described in patents US 6585944, 6468941, 6387338 and 6605264 included in its entirety in the present description by reference. However, the flexibility of the process of ion exchange provides the possibility of modifying and improving the properties of all currently known solid solution is in-based oxide, cerium oxide or cerium - zirconium.

Materials for HC, modified by way of the primary ion exchange, include compositions comprising balancing a significant amount of zirconium, with the aim of reducing energy recovery CE⁴⁺and activation energy of the reaction, providing mobility On the inside of the grille, as well as a sufficient amount of cerium to provide the desired capacity with respect to the storage of oxygen. In another preferred embodiment, the materials for HC should include a sufficient amount of the stabilizer, e.g., yttrium, rare earth element (La/Pr etc) or combinations thereof, to stabilize the solid solution in the preferred cubic crystalline phase.

Materials for HC, modified by way of the main exchange, should preferably differ essentially cubic fluorite structure that define conventional XRF. The percentage of MHC, having a cubic structure, both before and after the exchange is preferably more than about 95%, typically more than about 99%, and essentially 100% of a cubic structure on the basis of regular measurements (i.e. based on current measurement technology no measurable amount of tetragonal phase). Subjected to the exchange of MHC additionally differs in that it has a significantly increased long-term activity is in the oxidation-restoration namely provides easy storage of oxygen and increased capacity with respect to its allocation, which is described in detail in the filings of US 12/363310 and 12/363329.

Introduction to the catalyst such modified base metal materials CeZrOx, it has been found that provides a significant increase in activity in the catalytic oxidation of (especially) the CO and HC in the conditions of depleted fuel. Therefore, their introduction in conventional oxidation catalysts for diesel engines (CODE), as it was found, leads to unexpected and new improved catalytic properties in the context of a real application.

It has been found that a material containing base metal, can best way to apply or separately, or, more preferably, in conjunction with conventional containing PGM catalyst. Material containing base metal, can, therefore, be applied in a variety of configurations, for example, in the form of a single material, that is thoroughly mixed with the composition containing PGM; in the form of a separate layer of coating applied to or, more preferably, after the usual composition containing PGM. Optionally containing a base metal material can be applied as a uniform coating, or in the form of a solid or zone coating, which is applied to the portion of the total length of the monolith. Finally, the material content is a broad base metal, you can apply as a separate, second monolithic block that is located after the usual CODE containing PGM. In all of these configurations are achieved acceptable advantages in catalytic activity, and also improvement of the hydrothermal stability of the catalyst during the subsequent regulation of the composition of the EXHAUST gas.

Examples

Method for the preparation of samples a and b, used as test technology, was next. Preparing a suspension of aluminum oxide at a pH of about 4.5, and crushed to obtain d₅₀(the diameter of 50% of the particles)of from 4 to 6 μm, with a corresponding value of d₉₀. Then took a solution of platinum nitrate concentration and slowly diluted with the addition of a viscosity modifier to the desired dilution was then added dropwise the solution to the milled slurry of aluminum oxide. The suspension should have a pH below 6.0 before adding the metal and at the time it was added, the pH monitoring and preventing its reduction to values below 3.0 is achieved through the addition of base in required quantities. After adding metal pH was brought to 3.5 by addition of a base and a stirred suspension of 2 hours and Then was added dropwise a solution of palladium nitrate desired concentration, again during the addition of the metal monitored the pH and prevent the whether its reduction to values below 3.0 a reasonable addition of the base. Stirred the mixture for one hour to carry out a full chemisorption of metal. Then covered with a suspension of the monolith 1 reception, and progulivali at temperatures not less than 540°C in a period of time not less than one hour. Then took prepared in advance powder 2Cu-MHC (see application US 12/363310579 And in which the preparation of this material are described in detail) and spoke of him as a suspension with a minimum addition of deionized water, which is necessary to maintain the required viscosity/density, milled to obtain a value of d₅₀from 4 to 6 μm, and was confirmed by d₉₀. Was added the desired amount of solid powder of zeolite beta (adjusted for losses by fire), again with minimal addition of deionized water. Slightly milled mixture until smooth. Again confirmed the value of d₅₀and d₉₀. Checked the specific gravity and pH and regulate them so as to facilitate the coating process at one time. Then covered the monolith at once and progulivali at temperatures not less than 540°C. for a time not less than one hour.

The method of manufacture of the sample used as test technology, was next. Preparing a suspension of aluminum oxide at a pH of about 4.5, and crushed to obtain d₅₀(the diameter of 50% of the particles)of approx 4-6 microns, when the appropriate value of d₉₀. Then covered with a suspension of the monolith 1 reception, and progulivali at temperatures not less than 540°C. for a time not less than one hour. Then took prepared in advance powder 2Cu-MHC (see application US 12/363310, in which the preparation of this material are described in detail) and spoke of him as a suspension with a minimum addition of deionized water, which is necessary to maintain the required viscosity/density, milled to obtain a value of d₅₀from 4 to 6 μm, and was confirmed by d₉₀. Was added the desired amount of solid powder of zeolite beta (adjusted for losses by fire), again with minimal addition of deionized water. Slightly milled mixture until smooth. Again confirmed the value of d₅₀and d₉₀. Checked the specific gravity and pH and regulate them so as to facilitate the coating process at one time. Then covered the monolith at once and progulivali at temperatures not less than 540°C. for a time not less than one hour.

The method of preparation of a sample of N applied as test technology, was next. Was slowly added aluminum oxide and milled to a value of d₅₀component 7 µm (±1), d₉₀=20-25 μm, so that 100% of the particles had a size less than 60 microns. Mixed nitrate solution pay the s with the desired rheology modifiers for at least 30 min, and then was added dropwise to a suspension of aluminum oxide. The suspension should have a pH below 6.0 to and during the addition of the metal, the pH of the suspension was monitored or prevented falling pH values below 3.0 is a reasonable addition of the base. Stirred the resulting suspension for two hours and re-affirmed the value of d₁₀d₅₀and d₉₀. Then was added dropwise a solution of palladium nitrate, during the addition of the solution was monitored by a pH-value and prevent it from falling below a 3.0 a reasonable addition of the base. Stirred the resulting suspension for one hour to achieve chemisorption, then again confirmed the value of d₁₀d₅₀and d₉₀. Then preparing a suspension of the powder 2Cu-MHC in a minimum amount of deionized water required to maintain the viscosity /density of the suspension, and milled to a value of d₅₀from 4 to 6 μm was confirmed by the d₉₀. Added a powder of zeolite beta (adjusted for losses by fire) and was stirred for an additional 15 minutes Added to the mixture to suspension containing aluminum oxide and PGM directly into the funnel arising under stirring, while monitored the pH value. During the addition the pH should be in the range from 3 to 4. If the pH deviates from this interval were added when necessary, sour is at or base, this was supported by specific gravity and solids content as high as possible. Again confirmed the value of d₁₀d₅₀and d₉₀. Finally brought the pH to 3.0-3.5, and the weight was adjusted so as to hold the coating in one pass, then covered monolith at once and progulivali at a temperature of not less than 540°C. for a time not less than one hour.

Methods preparation of sample L, with the area covered CODE used as test technology, was next. Was slowly added aluminum oxide and milled to size d5o, part 7 µm (±1), d₉₀=20-25 μm, so that 100% of the particles had a size less than 60 microns. Mixed nitrate solution of platinum with the desired rheology modifiers for at least 30 min, and then was added dropwise to a suspension of aluminum oxide. The suspension should have a pH below 6.0 to and during the addition of the metal, the pH of the suspension was monitored or prevented falling pH values below 3.0 is a reasonable addition of the base. Stirred the resulting suspension for two hours and re-affirmed the value of d₁₀d₅₀and d₉₀. Then was added dropwise a solution of palladium nitrate, during the addition of the solution was monitored by a pH-value and prevent it from falling below a 3.0 a reasonable addition of the base. Displacement is ivali received the suspension for one hour to achieve chemisorption, then again confirmed the value of d₁₀d₅₀and d₉₀. Then was added a powder of zeolite beta (requires correction of the mass loss on ignition) in the funnel, resulting in the suspension under stirring, monitored pH, which should be from 3 to 4, if necessary, adjusted by adding a base. Supported specific gravity and solids content as possible high. Re-affirmed the value of d₁₀d₅₀and d₉₀, regulate pH (to a value of from 3.0 to 3.5) and the proportion so as to make the coating at one time; was coated and progulivali at temperatures not less than 540°C. for at least 1 h Then was preparing a suspension of the powder 2Cu-MHC in a minimum amount of deionized water required to maintain the viscosity /density of the suspension, and milled to a value of d₅₀from 4 to 6 μm was confirmed by the d₉₀. Added a powder of zeolite beta (adjusted for the weight loss during ignition) into the funnel that occur when mixing the suspension with a minimum amount of deionized water necessary to maintain the characteristics of the suspension. Slightly milled to obtain a homogeneous suspension and reconfirmed the value of d₁₀d₅₀and d₉₀. Finally brought the pH to 3.0-3.5, and the weight was adjusted so that about is if the floor in one pass then covered the monolith at once and progulivali at a temperature of not less than 540°C. for a time not less than one hour. Used plunger installation for coating, in order to facilitate the coating along the length of 50% of the length of the monolith.

Although the present invention described above with reference to typical preferred options, persons skilled in the art it will be clear that can be made of various modifications and equivalents can be substituted by other elements without deviating from the scope and General principles of the invention. In addition, it is possible to make many modifications to adapt a particular situation or material to the ideas set forth in the invention without deviating from its essential features. Therefore, it is assumed that the present invention is not limited to the specific preferred option, described as the best ways of implementing the present invention, but the invention will include all of the preferred alternatives falling within the scope of the appended claims.

Preferred variants of the present invention can be described as follows.

The oxidation catalyst, comprising: a first catalytically active metal (metals)deposited on the substrate, and the first catalytically active metal (m is of Tallaght) is chosen from the group of noble metals, including platinum, palladium, iridium, rhodium, ruthenium, and their alloys and combinations, and the second catalytically active component comprising phase containing cerium oxide, optionally modified by the introduction or addition of base metal and optionally a zeolite.

The oxidation catalyst containing precious metals, and containing a single catalytically active component, which includes containing the cerium oxide phase, optionally modified by the introduction or addition of base metal and optionally a zeolite.

The oxidation catalyst described above, in which a modified base metal component of the catalyst based on cerium oxide is a solid solution of cerium oxide and zirconium.

The oxidation catalyst described above, in which a modified base metal oxide of cerium, of zirconium is essentially phase pure solid solution (which is determined by the conventional method of x-ray phase analysis), having the properties of ionic conduction of oxygen and including

A. To about 95% zirconium;

B. To about 95% cerium;

C. Up to about 20% of a stabilizer selected from the group comprising rare earth metals, yttrium and mixtures thereof.

The oxidation catalyst described above, in which the modified becomes oronym metal terisolasi oxide contains one or more modifier base metals selected from the group comprising transition metals, alkali metals, alkaline earth metals and metals IIIB group.

The oxidation catalyst described above, in which the concentration of atoms introduced base metal is from about 0.01 to about 10% of the mass. from the maintenance phase of cerium oxide.

The oxidation catalyst described above, in which the concentration of atoms introduced base metal is from 0.1 to about 2.5%mascot content phase of cerium oxide.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide used in the same layer/pass, and that the catalyst containing PGM.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide used in the next layer/pass after catalyst layer containing PGM.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide is used as a layer located at the front layer/pass catalyst containing PGM.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide used in the form of a zone and the zone is located at the outlet of the oxidation catalyst.

The oxidation catalyst opican the th above in which a modified base metal terisolasi oxide used in the form of a zone and the zone is located at the entrance to the oxidation catalyst.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide is used in a separate, second monolith, and additionally in which the second monolith is located at the exit of the primary catalyst containing PGM.

The oxidation catalyst described above, in which a modified base metal terisolasi oxide is exposed to light and full regeneration in relation to the function of CO oxidation, which could be reduced as a result of accumulation of poisons derived SOx, during normal temperature associated with the engine of a car traveling on a highway, or cycles of regeneration of the DSF.

The oxidation catalyst described above, in which the base metal is introduced in the active oxidation-restoration terisolasi oxide in the form of a complex with ammonium hydroxide/ammonium complex cations of metal.

The oxidation catalyst described above, in which the base metal is introduced in the active oxidation-restoration material containing cerium oxide, in the form of an organic amine complex cations of metal.

The oxidation catalyst described above, to the torus base metal is introduced in the active oxidation-restoration material, containing cerium oxide in the form of a hydroxide of the metal cations.

The oxidation catalyst described above, containing a modified base metal-containing cerium oxide phase, in which terisolasi oxide product contains base metal in high degrees of dispersion, such that phase analysis by conventional methods of x-ray phase analysis confirms the presence of essentially pure cubic fluorite phase (>95%), and the additional phase modifying any bulk metal oxide is determined at the level of less than 5%, and the particle size of the modifier metal oxide defined by the broadening of the lines/method using the equation of Scherer, ranges from about 30 to about 100 Å.

The oxidation catalyst described above, containing a modified base metal phase containing cerium oxide, and terisolasi oxide component contains base metal in a high degree of dispersion, so that the phase analysis XRD confirms that promoted the material retains at least 95% cubic fluorite phase after hydrothermal oxidative aging at 1000°C.

The oxidation catalyst described above, which provided a significant promotion ionic conduction of oxygen aristarain oxide when neither the coy temperature, that is determined by the conventional methods of temperature-programmed recovery, compared to the unmodified aristarain oxide.

The oxidation catalyst described above, containing a modified base metal phase containing cerium oxide, in which the promotion of redox properties, a certain method (saved when the hydrothermal treatment at temperatures, making these systems suitable oxidation catalysts for diesel engines (CODE), i.e. the stability of the steps in oxidizing conditions at temperatures up to 1000°C in the presence of steam is higher in comparison with non-modified aristarain oxide.

A method of obtaining a oxidation catalyst, described above, comprising the following stages: introduction of non-precious metal in the active oxidation-restoration material on the basis of solid solutions CeZrOx, containing essentially pure cubic structure of fluorite type, with the introduction of active metal /him cations in solid solution is carried out in basic conditions using ammonium hydroxide/ammonium complex metal cations, or organic amine complex cations of metal, or using a hydroxide of the metal cations.

The oxidation catalyst obtained by the method described above.

Method of treatment of EXHAUST gas comprising passing the EXHAUST gas over the catalyst described above.

The catalytic device, comprising: a housing, which surrounds the substrate; an oxidation catalyst for engines with compression ignition, located on the substrate, and the oxidation catalyst includes a primary catalytically active metal (metals)deposited on the carrier, and the primary catalytically active metal (metals) are selected from the group of noble metals including platinum, palladium, iridium, rhodium, ruthenium, and their alloys and their mixtures, as well as secondary catalytically active component, which includes phase containing cerium oxide, optionally modified by the introduction or addition of base metal and optionally a zeolite.

Catalytic device described above, further comprising retaining material located between the housing and the substrate.

Key designations for the technology of obtaining CODE:

Sample A: Pass 1 of 67.1 g/l NR/150 20Pd 40Pt; Passage 2 of 91.5 g/l 2CuMXK3 30.5 g/l β SAR40

Sample: Pass 1 of 67.1 g/l NR/150 50Pd 10 Pt; Pass 2 of 91.5 g/l 2CuMXK3 30.5 g/l β SAR40

Sample From: Pass 1 of 67.1 g/l NR/150; Passage 2 of 91.5 g/l 2Cu-MXK3 30.5 g/l β SAR40

Sample D: Sales CODE @ 60 g/ft3 2:1 Pt:Pd

Sample F: Pass 1 of 67.1 g/l NR/150 7Pd 14Pt; Passage 2 of 91.5 g/l 2CuMXK3 30.5 g/l β SAR40

Sample F: Pass 1 of 67.1 g/LNR/150 10Pd 20Pt; Passage 2 of 91.5 g/l 2CuMXK3 30.5 g/l β SAR40

Sample G: Sales CODE @ 30 g/ft³2:1 Pt:Pd

Sample N: Pass 1 of 67.1 g/l NR/150 10Pd 20Pt of 91.5 g/l 2CuMXK3 30.5 g/l β SAR40

Sample J: the Passage of 167.2 g/l NR/150 30Pd 90Pt; Pass 2 91,65 g/l 2Cu - MXK3 30.5 g/l β SAR40

Sample: Pass 1 85,5 NR/150 Zr5 70Pt 47,78 g/l P SAR40; Pass 2 48,9 g/l 2Cu-MXK3

Sample L: Pass 1 85,5 g/l NR/150 Zr 5 10Pd 20Pt 18,33 g/l β SAR40; Pass 2 73,32 g/l 2Cu-MXK3 12.2 g/l β SAR40 covered at 50% of the length of the pattern

Sample M: Pass 1 85,5 g/l NR/150 Zr5 10Pd 20Pt 30,2 g/l β SAR40;

Pass 273,32 g/l 2Cu-MXK3 covered at 50% of the length of the pattern

1. The oxidation catalyst, including:
primary catalytically active metal (metals)deposited on the carrier, and the primary catalytically active metal (metals) are selected from the group of noble metals including platinum, palladium, iridium, rhodium, ruthenium, and their alloys, and combinations thereof, as well as secondary catalytically active component, which includes cubic fluorites CeZrO_xmaterial, the modified base metal, which is obtained by ion exchange between the surface of the cubic fluorite CeZrO_xmaterial and solution of non-precious metal and optionally a zeolite.

2. The oxidation catalyst not containing metals from the group of noble metals, in which a single catalytically active component comprises cubic fluorites CeZrO_xmate the ial group, the modified base metal, which is obtained by ion exchange between the surface of the cubic fluorite CeZrO_xmaterial and solution of non-precious metal and optionally a zeolite.

3. The oxidation catalyst according to claim 1 or 2, in which CeZrO_xmaterial, the modified base metal component is a solid solution of cerium oxide and zirconium.

4. The oxidation catalyst according to claim 1 or 2, in which cubic fluorites CeZrO_xmaterial, the modified base metal, is an essentially phase-pure solid solution (which is determined on the basis of the results of the conventional method of x-ray diffraction (RDA)), having the properties of ionic conduction of oxygen, and includes:
A. to about 95% zirconium;
B. to about 95% cerium;
C. up to about 20% of a stabilizer selected from the group comprising rare earth metals, yttrium and mixtures thereof.

5. The oxidation catalyst according to claim 1 or 2, in which cubic fluorites CeZrO_xmaterial, the modified base metal contains one or more modifier base metals selected from the group comprising transition metals, alkali metals, alkaline earth metals and metals IIIB group.

6. The oxidation catalyst according to claim 5, in which the concentration of atoms introduced n the noble metal is from about 0.01 to about 10 wt.% from the maintenance phase of cerium oxide.

7. The oxidation catalyst according to claim 5, in which the concentration of atoms introduced base metal is from 0.1 to about 2.5 wt.% from the maintenance phase of cerium oxide.

8. The oxidation catalyst according to claim 1, in which cubic fluorites CeZrO_xmaterial, the modified base metal used in the same layer/pass, and that the catalyst containing platinum group metals (PGM).

9. The oxidation catalyst according to claim 1, in which a modified base metal terisolasi oxide used in the next layer/pass after catalyst layer containing PGM.

10. The oxidation catalyst according to claim 1, in which cubic fluorites CeZrO_xmaterial, the modified base metal, applied as a layer/pass in front of the catalyst containing metals of platinovoi group (MPG).

11. The oxidation catalyst according to claim 1 or 2, in which cubic fluorites CeZrO_xmaterial, the modified base metal, used in the form of a zone and the zone is located at the outlet of the oxidation catalyst.

12. The oxidation catalyst according to claim 1 or 2, in which cubic fluorites CeZrO_xmaterial, the modified base metal, used in the form of a zone and the zone is located at the entrance to the oxidation catalyst.

13. The oxidation catalyst according to claim 1 or 2, in which ku is practical pluarity CeZrO _xmaterial, the modified base metal, used in a separate, second monolith, and additionally in which the second monolith is located at the exit of the primary catalyst containing PGM.

14. The oxidation catalyst according to claim 1 or 2, in which cubic fluorites CeZrO_xmaterial, the modified base metal is exposed to light and full regeneration in relation to the function of CO oxidation, which could be reduced as a result of accumulation of poisons derived SO_xduring normal temperature associated with the engine of a car traveling on a highway, or cycles of regeneration of the diesel particulate filter (DSF).

15. The oxidation catalyst according to claim 1 or 2, in which the base metal is introduced in the active oxidation-restoration cubic fluorites CeZrO_xmaterial in the form of a complex with ammonium hydroxide/ammonium complex cations of metal.

16. The oxidation catalyst according to claim 1 or 2, in which the base metal is introduced in the active oxidation-restoration cubic fluorites CeZrO_xmaterial in the form of an organic amine complex cations of metal.

17. The oxidation catalyst according to claim 1 or 2, in which the base metal is introduced in the active oxidation-restoration cubic fluorites CeZrO_xmaterial in the form of a hydroxide of the cation is in metal.

18. The oxidation catalyst according to claim 1 or 2, containing cubic fluorites CeZrO_xmaterial, the modified base metal containing phase in which cubic fluorites CeZrO_xthe material contains a base metal in a high degree of dispersion, such that phase analysis by conventional methods of x-ray phase analysis confirms the presence of essentially pure cubic fluorite phase (>95%), and the additional phase modifying any bulk metal oxide is determined at the level of less than 5%, and the particle size of the modifier metal oxide defined by the broadening of the lines/method using the equation of Scherer, ranges from about 30 to about 100 Å.

19. The oxidation catalyst according to claim 1 or 2, containing cubic fluorites CeZrO_xmaterial, the modified base metal containing phase in which terisolasi oxide component contains base metal in a high degree of disperati, so that phase analysis by x-ray diffraction (RDA) confirms that promoted the material retains at least 95% cubic fluorite phase after hydrothermal oxidative aging at 1000°C.

20. The oxidation catalyst according to claim 1 or 2, containing cubic fluorites CeZrO_xthe material, which is provided mean is inoe promotion ionic conduction of oxygen aristarain oxide at a low temperature, that is determined by the conventional methods of temperature-programmed recovery, compared to the unmodified aristarain oxide.

21. The oxidation catalyst according to claim 1 or 2, containing cubic fluorites CeZrO_xmaterial, the modified base metal containing phase in which the promotion of redox properties defined by temperature-programmed reduction with hydrogen (TPV), is saved by hydrothermal treatment at temperatures, making these systems suitable oxidation catalysts for diesel engines (CODE), i.e. the stability of the steps in oxidizing conditions at temperatures up to 1000°C in the presence of steam is higher compared to the unmodified aristarain oxide.

22. A method of obtaining a oxidation catalyst according to one or more of the preceding items, comprising the following stages: introduction of non-precious metal in the active in redox reactions, the material on the basis of solid solutions CeZrO_xcontaining essentially pure cubic fluorite structure, by introducing the active metal/him cations in solid solution under basic conditions in the form of ammonium hydroxide/ammonium complex metal cations, or organic amine complex cation is in metal, or in the form of hydroxide compounds of the cations of the metal.

23. The oxidation catalyst obtained by the method according to item 22.

24. Method of treatment of exhaust gases comprising passing the exhaust gases over a catalyst according to one or more of the preceding paragraphs.

25. The catalytic device, comprising: a housing, which surrounds the substrate; an oxidation catalyst according to claim 1 for engines with compression ignition, located on the substrate.

26. The catalytic device according to p. 25, further comprising retaining material located between the housing and the substrate.